Beruflich Dokumente
Kultur Dokumente
+
+ + +
2
3 2 2 3
8Fe 16HCO 8FeCO 8H O 8CO
(14.2)
+
+ + +
2
3 3 4 2
8Fe 16Fe(OH) 16OH 8Fe O 32H O (14.3)
+ +
1
2
3 2 4 3 2
3FeCO O Fe O 3CO
(14.4)
+ +
2 3 3 3 4 2
Fe O FeCO 4Fe O CO (14.5)
BIF also show an abundance of light carbon isotope signatures within the carbon
layers (Garrels et al. 1973; Baur et al. 1985) consistent with the initial presence of
microbial biomass during sedimentation. In addition, highly negative d
56
Fe values
in 2.9 Ga old magnetite (Yamaguchi et al. 2005), with comparable negative
317 14 Role of Microorganisms in Banded Iron Formations
fractionations as observed in experimental culture with dissimilatory Fe(III)-reducing
bacteria (Johnson et al. 2003), point towards the antiquity of such an anaerobic
respiratory pathway. Moreover, the recognition that a variety of deeply-branching
(and presumed very ancient) hyperthermophilic Bacteria and Archaea can reduce
Fe(III) to Fe(II) (Vargas et al. 1998), strengthens the likelihood that such a metabo-
lism occurred very early on Earth.
Assuming that sedimentation of biomass and Fe(III) took place during anoxy-
genic phototrophic or aerobic Fe(II) oxidation in the Archean, it could be argued
that the electrons present in the biomass associated with the sedimented Fe(III)
minerals could theoretically re-reduce all Fe(III) leaving no remains for a later
formation of hematite (Konhauser et al. 2005). However, since the Fe(III) oxide
hematite and also the mixed Fe(II)-Fe(III) oxide magnetite are major constituents
of many BIF it can be assumed that only minor amount of organic carbon were
initially deposited with the Fe(III)-rich sediment. Alternatively, the biomass and
electrons could have been removed from the sediment by Fe(III)-independent redox
processes, e.g. by fermentation or methanogenesis. Calculations by Konhauser
et al. (2005) showed that only about 3% of the biomass reached final burial. Indeed,
Konhauser et al. (2005) further suggested that some of the initially produced
biomass was transformed by hydrolysis and fermentation leading to a possible
Fig. 14.4 BIF thin section M1, Mamatwan Manganese Mine, Kuruman, North Cape Province, South
Africa. The sample is approximately 2.202.22 billion years old. Sample shows white magnetite
crystals in a jasperous fine grained matrix. The single magnetite crystals are subhedral to euhedral and
their sizes ranges from 1.0 to 0.5 mm. In the upper part of the section magnetite forms aggregates
with a size of up to 2 mm. Several crystals display narrow bright white rims identified as martite (see
arrows). The red color in the jasperous matrix comes from fine grained hematite particles
318 I. Koehler et al.
removal of electrons in form of reduced compounds (e.g. H
2
) away from the sediment
that otherwise would have been available to reduce Fe(III). Furthermore, some of
the H
2
or organic compounds could have been used by methanogens. The highly
negative d
13
C values of around 40 to 60 in 2.82.6 Ga old kerogens point to
intensive methane formation at that time (Hayes 1983).
Limitation of Microbial Processes in BIFs by
Nutrients and Trace Metals
Phosphate is essential to life due to its important role in many biomolecules such
as DNA, RNA and ATP, as well as a constituent in cellular membranes. It was
suggested that the strong affinity of phosphate to Fe(III) hydroxides could have
depleted the Archean ocean of phosphate leading to a phosphate crisis, i.e. con-
straining microbial activity due to limiting bioavailable concentrations of phos-
phate in the water column (Bjerrum and Canfield 2002). However, since Archean
oceans had high concentrations of dissolved and amorphous silica, the silica would
have competed with phosphate for sorption sites at the ferric hydroxide particle
1
Fe rich layer Fe rich layer
Fe rich layer
Fe rich layer
Si rich layer Si rich layer
2 3
Photoautotrophic
Fe(II) oxidation
Photoautotrophic
Fe(II) oxidation
precipitating Si
Fig. 14.5 Possible deposition of alternating iron and silicate mineral layers triggered by tempera-
ture fluctuations in the ocean water: (1) and (3) Moderate/higher temperatures yield relatively high
photoautotrophic bacteria oxidation rates and thus iron(III) mineral formation. Therefore, biomass
and Fe(III) settle together to the seafloor. (2) With decreasing temperatures photoautotrophic
oxidation rates slow down and at the same time lower temperatures initiate abiotic Si precipitation
from Si oversaturated ocean water. Si minerals then settle to the seafloor
319 14 Role of Microorganisms in Banded Iron Formations
surface lowering sorption of phosphate compared to silica-free systems. Additionally,
the co-precipitation of iron and silica changes the particles point of zero charge
(PZNC) also lowering phosphate binding and phosphate removal from the ocean
water (Konhauser et al. 2007). Overall, it was therefore suggested that phosphate in
the Archean was probably not limiting.
Besides nutrients such as phosphate, trace metals are important for microorgan-
isms due to their role as metal-cofactors. Although the microorganisms usually
need only small quantities, trace metals such as nickel, copper, and cobalt can rep-
resent a limiting factor for microbial growth. A possible approach to constrain the
plausibility of a certain bacterial activity at the time of BIF formation is therefore
to estimate concentrations of trace metals required by a certain physiological group
of microbes in the Archean ocean from the abundance of these trace metals in BIF.
However, to use this approach to constrain certain microbial processes, several
questions have to be addressed.
1. Is the trace metal distribution in BIF representative of the composition of the
Archean ocean or has there been major remobilization due to diagenesis and/or
metamorphism?
2. Do certain trace metals show different sorption behavior to abiogenic versus
biogenic Fe(III) minerals and is there a difference in co-precipitation during abi-
otic versus biotic Fe(II) oxidation?
3. Is there an inuence by silica on the sorption and co-precipitation behavior of
trace metals?
Recently, analysis of Ni concentrations in BIF, in combination with quantification
of Ni sorption behavior to Fe(III) (hydr)oxides (similar to the ones assumed to be
the primary minerals of BIF), suggested a decrease in the amount of bioavailable
Ni around 2.7 Ga ago probably due to a cooling of the mantle. As a consequence,
microbial methane production could have slowed since Ni is essential for these
microbes ((Jaun and Thauer 2007), potentially initiating the so-called Great
Oxidation Event around 2.4 Ga (Konhauser et al. 2009). Another potentially inter-
esting trace metal is cobalt, which has been identified as being involved in Fe(II)
oxidation in phototrophic Fe(II)-oxidizing bacteria and thus possibly limited
photoferrotrophic activity in the Archean (Jiao et al. 2005). However, sorption
behaviour of Co to abiogenic and biogenic Fe(III) (hydr)oxides has not been cor-
related with BIF Co concentrations thus far.
Mechanisms of Altering Iron and Silica Mineral
Layering A Potential Role of Microorganisms?
BIF show a characteristic layering of Fe-rich and silica/carbonate-rich bands. The
thickness of the layers varies between micro-scale to meter-thick units (Trendall
1968; Beukes and Klein 1992; Klein 2005) and some BIF show a wide lateral
continuity of up to hundreds of kilometers. This raises the question of whether the
320 I. Koehler et al.
alternating banding has a unifying trigger (Posth et al. 2008), and whether the
precipitation of either iron or silica somehow influences the formation of the other.
It has been suggested that the layering is due to seasonal stratification or yearly
climate cycles (Morris 1993), in which periodic upwelling or hydrothermal pulsation
of Fe(II)-rich waters was punctuated by seasonal evaporation of silica (Holland
1973; Garrels 1987; Jacobsen and Pimental-Klose 1988; Siever 1992).
However, these models have been questioned since they do not explain the
lateral banding of both Fe(III) and silica minerals. Additionally, they do not explain
why iron and silica do not co-precipitate to a large extent (Trendall 1968; Garrels
1987; Morris 1993). Accordingly, a new model has been suggested that links tem-
perature-induced bacterial Fe(II)-oxidation to abiotic silicification as a way of
explaining the banding (Posth et al. 2008). The activity of phototrophic Fe(II)-
oxidizing bacteria (Fe(II) oxidation rates) shows a strong temperature dependency
(Hegler et al. 2008; Posth et al. 2008). When the bacteria were incubated under
changing temperature conditions and in the presence of silica, at water tempera-
tures of 2530C, the Fe(II) oxidation rate and the ferric hydroxide precipitation
was high. Below and above these temperatures, Fe(II) oxidation and the precipita-
tion of the biogenic iron(III) minerals decreased. At lower temperatures when
Fe(III) mineral precipitation decreased, however, the precipitation of amorphous
silica was triggered. As temperatures increased to 2530C, Fe(III) minerals were
again precipitated by the Fe(II)-oxidizing phototrophs, effectively allowing the
alternating layering of silica and Fe minerals. Interestingly, the rate of Fe(II) oxida-
tion was not affected by the silica and Fe(III) precipitation seems to be decoupled
from silica precipitation. This is probably due to the change in Fe(III) mineral sur-
face charge from positive to negative due to the sorption of cell organic matter
preventing silica sorption (Posth et al. 2008). This decoupling suggests that a sepa-
rate deposition of Fe-rich and silica-rich layers in BIF could have been triggered by
one unifying parameter, temperature.
These findings raise the question of whether ocean temperature cycles in the
Archean existed and were strong enough to trigger the banding. Estimates of water
temperature in the Archean are poorly constrained, and range from 10C to 85C
(Knauth and Lowe 2003; Knauth 2005; Robert and Chaussidon 2006; Kasting et al.
2006; Jaffrs et al. 2007; Shields and Kasting 2007). An additional difficulty in
constraining these past temperature is the high potential for diagenetic overprinting,
which might distort the data. Based on the most recent interpretations, the general
climate in the Archean was around 1033C (Kasting et al. 2006) and consequently,
mesophilic Fe(II)-oxidizing phototrophs, as used in the experiments by Posth et al.
(2008), would prosper in such an environment.
Nevertheless, two independent lines of evidence suggest that such temperature
fluctuations took place in the ancient ocean. First, modern ocean temperature cycles
depend on incoming currents and seasonal variations and show temperature
changes as needed for the effects observed by Posth et al. (2008). Second, a tilt in
Earths axis (obliquity) could have caused seasonal temperature changes (Laskar
and Robutel 1993).
321 14 Role of Microorganisms in Banded Iron Formations
Conclusions
Banded iron formations not only serve as possible archives for the Precambrian
atmosphere and hydrosphere but they shed insights into the biotic processes occur-
ring at that time. It is generally believed that the large amounts of oxidized Fe pres-
ent in the BIFs were formed by oxidation of hydrothermal Fe(II). The oxidation of
the Fe(II) after 2.72.5 Ga ago could be due to cyanobacterial O
2
, however, the
formation of BIF older than 2.72.5 Ga requires an anoxic mechanism for Fe(II)
oxidation. Currently, anoxygenic photosynthetic bacteria provide the most plausi-
ble explanation of Fe(III) mineral deposition in the anoxic Archean. The role of
microorganisms in BIF deposition also goes beyond providing the O
2
for Fe(II)
oxidation or direct Fe(II) oxidation. Biomass and ferric hydroxides deposited at the
sea floor provide the necessary substrates for Fe(III)-reducing bacteria, fermenters
and methanogens. These microorganisms probably reworked the sediments to a
significant extent before ultimate lithification.
Acknowledgements This work was supported by research grants from the German Research
Foundation (DFG) made to AK (KA 1736/2-1, 2-2, 4-1, and 12-1), funding from the DFG and the
University of Tuebingen to IK, and the Natural Sciences and Engineering Research Council of
Canada to KK. We would also like to thank Nicole Posth and Merle Eickhoff for helpful
comments.
References
Anbar AD, Duan Y, Lyons TW, Arnold GL, Kendall B, Creaser RA, Kaufman AJ (2007) A whiff
of oxygen before the great oxidation event? Science 317:19031906
Ayres DE (1972) Genesis of iron-bearing minerals in banded iron formation mesobands in the
Dales Gorge member, Hamersley Group, Western Australia. Econ Geol 67:12141233
Baur ME, Hayes JM, Studley SA, Walter MR (1985) Millimeter-scale variations of stable isotope
abundances in carbonates from banded iron formations in the Hamersley Group of Western
Australia. Economic Geol 80:270282
Berner RA (1969) Goethite stability and the origin of red beds. Geochim Cosmochim Acta
33:267273
Beukes NJ, Klein C (1992) Models for iron-formation deposition. In: Schopf JW, Klein C (eds)
The proterozoic biosphere: a multidisciplinary study. University of Cambridge Press,
Cambridge, UK, pp 147151
Bjerrum CJ, Canfield DE (2002) Ocean productivity before about 1.9 Gyr ago limited by phos-
phorus adsorption onto iron oxides. Nature 417:159162
Brasier MD, Green OR, Jephcoat AP, Kleppe AK, Van Kranendonk MJ, Lindsay JF, Steele A,
Grassineau NV (2002) Questioning the evidence for Earths oldest fossils. Nature 416:7681
Braterman PS, Cairns-Smith AG, Sloper RW (1983) Photo-oxidation of hydrated Fe
2+
significance
for banded iron formations. Nature 303:163164
Brocks JJ, Logan GA, Buick R, Summons RE (1999) Archean molecular fossils and the early rise
of eukaryotes. Science 285:10331036
Buick R (1992) The antiquity of oxygenic photosynthesis: evidence for stromatolites in sulphate-
deficient Archaean lakes. Science 255:7477
322 I. Koehler et al.
Cairns-Smith AG (1978) Precambrian solution photochemistry, inverse segregation, and banded
iron formations. Nature 276:807808
Cloud P (1973) Paleoecological significance of the banded iron-formation. Econ Geol
68:11351143
Crowe SA, Jones C, Katsev S et al (2008) Photoferrotrophs thrive in an Archean Ocean analogue.
Proc Natl Acad Sci USA 105:1593815943
Farquhar J, Bao H, Thiemens M (2000) Atmospheric influence of Earths earliest sulfur cycle.
Science 289:756758
Francois LM (1986) Extensive deposition of banded iron formations was possible without photo-
synthesis. Nature 320:352354
Frei R, Gaucher C, Poulton SW, Canfield DE (2009) Fluctuations in Precambrian atmospheric
oxygenation recorded by chromium isotopes. Nature 461:250253
Garrels RM, Perry EA Jr, MacKenzie FT (1973) Genesis of Precambrian iron-formations and the
development of atmospheric oxygen. Econ Geol 68:11731179
Garrels RM (1987) A Model for the deposition of the microbanded Precambrian iron formations.
American Journal of Science 287:81106
Gross GA (1965) Geology of iron deposits in Canada, Volume 1. General geology and evaluation
of iron deposits, Geological Survey of Canada Economic Report, 22
Han T-M (1978) Microstructures of magnetite as guides to its origin in some Precambrian iron-
formations. Fortschr Mineral 56:105142
Hayes JM (1983) Geochemical evidence bearing on the origin of aerobiosis, a speculative hypoth-
esis. In: Schopf JW, Klein C (eds) Earths earliest biosphere, its origins and evolution.
Princeton University Press, Princeton, NJ, pp 291301
Hegler F, Posth NR, Jiang J, Kappler A (2008) Physiology of phototrophic iron(II)- oxidizing
bacteria-implications for modern and ancient environments. FEMS Microbiol Ecol 66:250260
Heising S, Richter L, Ludwig W, Schink B (1999) Chlorobium ferrooxidans sp. nov., a phototrophic
green sulfur bacterium that oxidizes ferrous iron in coculture with a Geospirillum sp. strain.
Arch Microbiol 172:116124
Hoffman PF, Schrag DP (2000) Snowball Earth. Sci Am 282(January):6875
Holland HD (1973) The oceans: a possible source of iron in iron-formations. Econ Geol
68:11691172
Jacobsen SB, Pimentel-Klose MR (1988) A Nd isotopic study of the Hamersley and Michipicoten
banded iron formations: the source of REE and Fe in Archean oceans. Earth Planet Sci Lett
87:2944
Jaffrs JBD, Shields GA, Wallmann K (2007) The oxygen isotope evolution of seawater: a critical
review of a long-standing controversy and an improved geological water cycle model for the
past 3.4 billion years. Earth Sci Rev 83:83122
James HL (1954) Sedimentary facies of iron-formation. Econ Geol 49:236294
James HL (1966) Chemistry of the iron-rich sedimentary rocks. In: Fleischer M (ed) Data of
geochemistry, 6th edn. Paper 440-W. US Govt. Printing Office, Washington, DC
Jaun B, Thauer RK (2007) Nickel and its surprising impact in nature. In: Sigel A, Sigel H, Sigel
RKO (eds) Metal ions in life sciences, vol 2. Wiley, Chichester, UK, pp 323356
Jiao Y, Kappler A, Croal LR, Newman DK (2005) Isolation and characterization of a genetically
tractable photoautotrophic Fe(II)-oxidizing bacterium, Rhodopseudomonas palustris Strain
TIE-1. Appl Environ Microbiol 71:110
Johnson CM, Beard BL, Beukes NJ, Klein C, OLeary JM (2003) Ancient geochemical cycling in
the Earth as inferred from Fe isotope studies of banded iron formations from the Transvaal
craton. Contrib Mineral Petrol 144:523547
Kappler A, Pasquero C, Konhauser KO, Newman DK (2005) Deposition of banded iron forma-
tions by anoxygenic phototrophic Fe(II)-oxidizing bacteria. Geology 33:865868
Kasting JF, Howard MT, Wallmann K, Veizer J, Shields G, Jaffrs J (2006) Paleoclimates, ocean
depth, and the oxygen isotopic composition of seawater. Earth Planet Sci Lett 252:8293
Kholodov VN (2008) Siderite formation and evolution of sedimentary iron ore deposition in the
Earths history. Geol Ore Deposits 50:299319
323 14 Role of Microorganisms in Banded Iron Formations
Klein C (2005) Some Precambrian Banded Iron Formations (BIFs) from around the world: their
age, geologic setting, mineralogy, metamorphism, geochemistry, and origin. Am Mineral
90:14731499
Klein C, Beukes NJ (1989) Geochemistry and sedimentology of a facies transition from limestone
to iron-formation deposition in the Early Proterozoic Transvaal Supergroup, South Africa.
Econ Geol 84:17331774
Knauth LP (2005) Temperature and salinity history of the Precambrian Ocean: implications for
the course of microbial evolution. Palaeogeogr Palaeoclimatol Palaeoecol 219:5369
Knauth PL, Lowe DR (2003) High Archaen climatic temperature inferred from oxygen isotope
geochemistry of cherts in the 3.5 Ga Swaziland Supergroup, South Africa. Geol Soc Am Bull
115:566580
Konhauser KO, Hamade T, Raiswell R, Morris RC, Ferris FG, Southam G, Canfield DE (2002)
Could bacteria have formed the Precambrian banded iron formations? Geology
30:10791082
Konhauser KO, Newman DK, Kappler A (2005) The potential significance of microbial Fe(III)
reduction during deposition of Precambrian banded iron formations. Geobiology 3:167177
Konhauser KO, Amskold L, Lalonde SV, Posth NR, Kappler A, Anbar A (2007) Decoupling
photochemical Fe(II) oxidation from shallow-water deposition. Earth Planet Sci Lett
258:87100
Konhauser KO, Pecoits E, Lalonde SV, Papineau D, Nisbet EG, Barley ME, Arndt NT, Zahnle K,
Kamber BS (2009) Oceanic nickel depletion and a methanogen famine before the great oxida-
tion event. Nature 458:750754
Krape B, Barley ME, Pickard AL (2003) Hydrothermal and resedimented origins of the precursor
sediments to banded iron formation: sedimentological evidence from the Early Paleoproterozoic
Brockman supersequence of Western Australia. Sedimentology 50:9791011
Laskar J, Robutel P (1993) The chaotic obliquity of the planets. Nature 361:608612
McConchie D (1987) The geology and geochemistry of the Joffre and Whaleback Shale members
of the Brockman iron formation, Western Australia. In: Appel PWU, LaBerge GL (eds)
Precambrian iron-formations. Theophrastus, Athens
Mojzsis SJ (2003) Probing early atmospheres. Nature 425:249251
Mojzsis SJ, Arrhenius G, McKeegan KD, Harrison TM, Nutman AP, Friend CRL (1996) Evidence
for life on Earth before 3, 800 million years ago. Nature 384:5559
Morris RC (1993) Genetic modelling for banded iron-formation of the Hamersley Group, Pilbara
Craton, Western Australia. Precambrian Res 60:243286
Pavlov AA, Kasting JF (2002) Mass-independent fractionation of sulfur isotopes in Archean sedi-
ments: strong evidence for an anoxic Archean atmosphere. Astrobiology 2:2741
Perry EC, Tan FC, Morey GB (1973) Geology and stable isotope geochemistry of the Biwabik
iron formation, northern Minnesota. Econ Geol 68:11101125
Posth NR, Hegler F, Konhauser KO, Kappler A (2008) Alternating Si and Fe deposition caused
by temperature fluctuations in Precambrian oceans. Nat Geosci 10:703708
Posth NR, Konhauser KO, Kappler A (2010a) Microbiological processes in BIF deposition. In:
Glenn C, Jarvis I (eds) Authigenic minerals: sedimentology, geochemistry, origins, distribution
and applications. Journal of Sedimentology IAS Special Publication Series (in press)
Posth NR, Konhauser KO, Kappler A (2010b) Banded iron formations. In: Thiel V, Reitner J (eds)
Encyclopedia of geobiology. Springer, Hiedelberg (in press)
Rashby SE, Sessions AL, Summons RE, Newman DK (2007) Biosynthesis of 2-ethylbacterio-
hopanepolyols by an anoxygenic phototroph. Proc Natl Acad Sci USA 104:1509915104
Rasmussen B, Buick R (1999) Redox state of the Archean atmosphere: evidence from detrital
heavy metals in ca. 32502750 Ma sandstones from the Pilbara Craton. Aust Geol
27:115118
Robert F, Chaussidon M (2006) A Paleotemperature curve for the Precambrian oceans based on
silicon isotopes in cherts. Nature 443:969
Runnegar B (1991) Precambrian oxygen levels estimated from the biochemistry and physiology
of early eukaryotes. Palaeogeogr Palaeoclimatol Palaeoecol 71:97111
324 I. Koehler et al.
Schopf JW (1993) Microfossils of the early Archean Apex Chert: new evidence of the antiquity
of life. Science 260:640646
Shields GA, Kasting JF (2007) Palaeoclimatology: evidence for hot early oceans? Nature
447:E1
Siever R (1992) The silica cycle in the Precambrian. Geochim Cosmochim Acta 56:32653272
Straub KL, Rainey FR, Widdel F (1999) Rhodovulum iodosum sp. nov. and Rhodovulum
robiginosum sp. nov., two new marine phototrophic ferrous-iron-oxidizing purple bacteria. Int
J Syst Bacteriol 49:729735
Summons RE, Jahnke LL, Hope JM, Logan GA (1999) 2-Methylhopanoids as biomarkers for
cyanobacterial oxygenic photosynthesis. Nature 400:554557
Tice MM, Lowe DR (2004) Photosynthetic microbial mats in the 3,416 Myr old ocean. Nature
431:549552
Trendall AF (1968) Three Great Basins of Precambrian banded iron formation deposition: a sys-
tematic comparison. Geol Soc Am Bull 79:15271544
Vargas M, Kashefi K, Blunt-Harris EL, Lovely DR (1998) Microbiological evidence for Fe(III)
reduction on early Earth. Nature 395:6567
Walter XA, Picazo A, Miracle RM, Vicente E, Camacho A, Aragno M, Zopfi J (2009) Anaerobic
microbial iron oxidation in an iron-meromictic lake. Geochim Cosmochim Acta
73(13):A1405
Widdel F, Schnell S, Heising S, Ehrenreich A, Assmus B, Schink B (1993) Ferrous iron oxidation
by anoxygenic phototrophic bacteria. Nature 362:834836
Xiong J (2006) Photosynthesis: what color was its origin? Genome Biol 7:245
Yamaguchi KE, Johnson CM, Beard BL, Ohmoto H (2005) Biogeochemical cycling of iron in the
Archean Paleoproterozoic Earth: constraints from iron isotope variations in sedimentary rocks
from the Kaapvaal and Pilbara Cratons. Chem Geol 218:135169